EP2404311A1 - Iii-nitride light emitting device incorporating boron - Google Patents

Iii-nitride light emitting device incorporating boron

Info

Publication number
EP2404311A1
EP2404311A1 EP10704198A EP10704198A EP2404311A1 EP 2404311 A1 EP2404311 A1 EP 2404311A1 EP 10704198 A EP10704198 A EP 10704198A EP 10704198 A EP10704198 A EP 10704198A EP 2404311 A1 EP2404311 A1 EP 2404311A1
Authority
EP
European Patent Office
Prior art keywords
light emitting
layer
lattice constant
gai
layers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP10704198A
Other languages
German (de)
French (fr)
Other versions
EP2404311B1 (en
Inventor
Melvin B. Mclaurin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke Philips NV
Lumileds LLC
Original Assignee
Koninklijke Philips Electronics NV
Philips Lumileds Lighing Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Koninklijke Philips Electronics NV, Philips Lumileds Lighing Co LLC filed Critical Koninklijke Philips Electronics NV
Publication of EP2404311A1 publication Critical patent/EP2404311A1/en
Application granted granted Critical
Publication of EP2404311B1 publication Critical patent/EP2404311B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
    • H01S5/00—Semiconductor lasers
    • H01S5/30—Structure or shape of the active region; Materials used for the active region
    • H01S5/34—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers
    • H01S5/343—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/12—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/04—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction
    • H01L33/06—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a quantum effect structure or superlattice, e.g. tunnel junction within the light emitting region, e.g. quantum confinement structure or tunnel barrier

Definitions

  • This invention relates to the field of semiconductor light emitting devices, and more specifically to Ill-nitride light emitting devices.
  • LEDs light emitting diodes
  • RCLEDs resonant cavity light emitting diodes
  • VCSELs vertical cavity laser diodes
  • edge emitting lasers are among the most efficient light sources currently available.
  • Materials systems currently of interest in the manufacture of high-brightness light emitting devices capable of operation across the visible spectrum include Group III -V semiconductors, particularly binary, ternary, and quaternary alloys of gallium, aluminum, indium, and nitrogen, also referred to as Ill-nitride materials.
  • Ill-nitride light emitting devices are fabricated by epitaxially growing a stack of semiconductor layers of different compositions and dopant concentrations on a sapphire, silicon carbide, Ill-nitride, composite, or other suitable substrate by metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), or other epitaxial techniques.
  • MOCVD metal-organic chemical vapor deposition
  • MBE molecular beam epitaxy
  • the stack often includes one or more n- type layers doped with, for example, Si, formed over the substrate, one or more light emitting layers in an active region formed over the n-type layer or layers, and one or more p-type layers doped with, for example, Mg, formed over the active region. Electrical contacts are formed on the n- and p-type regions.
  • Ill-nitride devices are often grown on sapphire or SiC substrates.
  • an n-type GaN region is grown on the substrate, followed by an InGaN active region, followed by an AlGaN or GaN p-type region.
  • the difference in lattice constant between the non-III-nitride substrate and the III -nitride layers, as well as the difference in lattice constant between Ill-nitride layers of different composition causes strain in the device.
  • the strain energy due to lattice mismatch can cause defects and decomposition of the InGaN active region, which may cause poor device performance. Since the strain energy is a function of both the composition of the InGaN light emitting layer (which determines the amount of strain) and the thickness of the light emitting layer, both the thickness and composition are limited in conventional Ill-nitride devices.
  • boron which is a 'light' element, could, in principle, compensate for the strain induced by a high fraction of 'heavy' indium in InGaN-based light emitters and could provide lattice matching for BGaN grown on AlN and SiC substrates.” See, for example, the first paragraph in the first column on the first page of Ougazzaden et al.
  • An object of the invention is to provide a III -nitride device where at least one layer in the light emitting region includes boron.
  • Embodiments of the invention include a III- nitride semiconductor structure comprising a light emitting region disposed between an n-type region and a p-type region. At least one layer in the light emitting region is B x (In y Gai_ y )i_ x N.
  • the B x (In y Gai_ y )i_ x N layer has a band gap energy and a bulk lattice constant corresponding to a lattice constant of a relaxed layer having a same composition as the B x (In y Gai_ y )i_ x N light emitting layer.
  • An InGaN layer having a same band gap energy as the B x (In y Gai_ y )i_ x N layer has a bulk lattice constant corresponding to a lattice constant of a relaxed layer having a same composition as the InGaN layer.
  • the bulk lattice constant of the B x (In y Gai_ y )i_ x N layer is less than the bulk lattice constant of the InGaN layer.
  • Fig. 1 illustrates a portion of a III -nitride light emitting device according to embodiments of the invention.
  • Figs. 2, 3, and 4 are plots of ideal band gap energy as a function of position for portions of Ill-nitride devices according to embodiments of the invention.
  • Fig. 5 is a plot of band gap energy as a function of lattice constant for binary, ternary, and quaternary alloys of aluminum, boron, gallium, indium, and nitrogen.
  • Fig. 6 is a cross sectional view of a portion of a Ill-nitride device mounted in flip chip configuration on a mount.
  • Fig. 7 is an exploded view of a packaged light emitting device.
  • Fig. 8 is a plot of BN composition as a function of InN composition for BInGaN layers that are lattice-matched to GaN.
  • boron is incorporated into one or more layers of a Ill-nitride device. Incorporating boron into layers of a Ill-nitride device, particularly in the active region of the device, may reduce the strain in the device, which may improve the performance of the device.
  • Fig. 1 illustrates an embodiment of the invention.
  • a first single crystal layer 12 is grown over a suitable growth substrate 10.
  • the first single crystal layer 12 determines the lattice constant of all the Ill-nitride layers grown over it.
  • the composition and growth conditions of first single crystal layer 12 may determine the lattice constant.
  • An active or light emitting region 16 is grown over the first single crystal layer 12, sandwiched between an n-type region 14 and a p-type region 18.
  • N-type region 14 and first single crystal layer 12 may include multiple layers of different compositions and dopant concentration including, for example, preparation layers such as buffer layers or nucleation layers grown before or after first single crystal layer 12, which may be n-type or not intentionally doped, release layers designed to facilitate later release of the growth substrate or thinning of the semiconductor structure after substrate removal, and n- or even p-type device layers designed for particular optical or electrical properties desirable for the light emitting region to efficiently emit light.
  • a portion of n-type region 14 closest to the growth substrate is the first single crystal layer grown in the device, and a separate first single crystal layer 12 is omitted.
  • P-type region 18 is grown over light emitting region 16. Like the n-type region, the p-type region may include multiple layers of different composition, thickness, and dopant concentration, including layers that are not intentionally doped, or n-type layers.
  • Active region 16 is grown over n-type region 14.
  • suitable light emitting regions include a single thick or thin light emitting layer, or a multiple quantum well light emitting region including multiple thin or thick quantum well light emitting layers separated by barrier layers.
  • a multiple quantum well light emitting region may include multiple light emitting layers, each with a thickness of 25 A or less, separated by barriers, each with a thickness of 100 A or less.
  • the thickness of each of the light emitting layers in the device is thicker than 50 A.
  • the light emitting region of the device is a single, thick light emitting layer with a thickness between 50 and 600 A, more preferably between 100 and 400 A.
  • the optimal thickness may depend on the number of defects within the light emitting layer.
  • the concentration of defects in the light emitting region is limited to less than 10 9 cm “2 in some embodiments, to less than 10 8 cm “2 in some embodiments, to less than 10 7 cm “2 in some embodiments, and to less than 10 6 cm “2 in some embodiments.
  • At least one light emitting layer in the device is doped with a dopant such as Si to a dopant concentration between IxIO 18 cm “3 and IxIO 20 cm “3 .
  • Si doping may further reduce the strain in the light emitting layer.
  • the light emitting layer or layers are not intentionally doped.
  • Figs. 2-4 illustrate ideal band gap as a function of position for portions of light emitting devices according to embodiments of the invention.
  • the band gaps illustrated are ideal, and therefore a function of composition only. Effects in real devices which may distort the band gap diagram, such as polarization, are not illustrated in Figs. 2-4.
  • active region 16 includes a single light emitting layer.
  • the light emitting layer may be a quaternary alloy of boron, indium, gallium, and nitrogen.
  • the boron and indium composition are selected for the desired band gap in the light emitting layer, which determines the wavelength of emitted light.
  • the portion of n-type region 14 adjacent active region 16 may be, for example, GaN or InGaN.
  • the portion of p- type region 18 adjacent active region 16 may be, for example, GaN, InGaN, or AlGaN.
  • n-type region 14 and p-type region 18 are selected such that the change in band gap between n-type region 14 and active region 16, and between active region 16 and p- type region 18, sufficiently confines electrons and holes in the active region.
  • the difference between the band gap energy in the light emitting layers of active region 16 and the portions of n- and p-type regions 14 and 18 immediately adjacent the active region may be at least several times kT, which is 0.026 eV at room temperature.
  • the difference may be at least 0.1 eV in some embodiments, at least 0.15 eV in some embodiments.
  • active region 16 includes a single light emitting layer, as described above in reference to Fig. 2.
  • the composition in one or both of the n-type region and the p-type region adjacent the light emitting layer is graded.
  • the portion of n-type region 14 adjacent graded region 14a may be GaN.
  • the composition may be graded from GaN to InGaN to the BInGaN composition in light emitting layer 16.
  • the portion of p-type region 18 adjacent graded region 18a may be GaN.
  • the composition may be graded from the BInGaN composition in light emitting layer 16 to InGaN to GaN.
  • composition profile on either side of the active region 16 need not be symmetrical as illustrated in Fig. 3, and any graded region need not be linearly graded, as illustrated in Fig. 3.
  • the composition on only one side of active region 16 is graded.
  • a graded region as illustrated in Fig. 3 is combined with a step change in composition, as illustrated in Fig. 2.
  • the composition may be graded from GaN to InGaN in graded region 14a, then changed from InGaN to the BInGaN composition in active region 16 in a step change.
  • active region 16 is a multiple quantum well active region with quantum well layers separated by one or more barrier layers. Though three quantum well layers 16a and two barriers 16b are shown in Fig. 4, more or fewer quantum well layers may be included in active region 16.
  • Quantum wells 16a may be BInGaN, where the boron and indium compositions are selected for the desired band gap in the light emitting layer.
  • Barrier layers 16b may be GaN, or InGaN at an indium composition having a band gap larger than the band gap in quantum wells 16a.
  • quantum wells 16a may be InGaN and barrier layers 16b may be BInGaN with a boron and indium composition selected to have a band gap larger than the band gap in quantum wells 16a.
  • the multiple quantum well active region illustrated in Fig. 4 may be combined with graded composition n- and/or p-type regions, as described above in the text accompanying Fig. 3.
  • a Ill-nitride layer in a device may be characterized by lattice constant.
  • the "in-plane” lattice constant refers to the actual lattice constant of a layer within the device.
  • the “bulk” lattice constant refers to an ideal lattice constant of relaxed, free-standing material of a given composition. When the in-plane and bulk lattice constants of a layer are the same, the layer is relaxed, or free of strain.
  • strain
  • ⁇ I (a ⁇ i ⁇ e - at, u ik) I / at, u ik-
  • strain may be measured using lattice constants other than the a-lattice constant, or using more than one lattice constant. Layers may be lattice-matched for one lattice constant, and strained for another lattice constant.
  • the composition in BInGaN light emitting layers are selected to have a bulk lattice constant that matches or is close to the in-plane lattice constant of first single crystal layer 12, shown in Fig. 1.
  • First single crystal layer 12 is often GaN, with an in-plane a-lattice constant of about 3.189 A.
  • the band gap E g of an alloy A x Bi_ x C may be expressed by:
  • E g ABC xE g AC + (l-x)E g BC + x(l-x)B,
  • B band gap bowing parameter, which describes any non-zero curvature of a band gap vs. composition line.
  • the bowing parameter is zero
  • the relationship between band gap and composition is referred to as a Vegard's law relationship.
  • Ternary alloys of aluminum, indium, gallium, and nitrogen (i.e., alloys that do not contain boron) at low indium compositions (for example, less than 30% InN) have bulk lattice constants that typically follow Vegard's law.
  • Fig. 5 is a plot of lattice constant as a function of band gap energy for several III- nitride alloys.
  • GaN, and ternary alloys of aluminum, gallium, indium, and nitrogen are represented by lines 24 and 26. Shaded region 20 represents quaternary alloys of aluminum, gallium, indium, and nitrogen. While it is possible to grown AlGaInN alloys that are lattice matched to GaN, as illustrated in Fig. 5, they all have band gaps larger than GaN, making them potentially useful for UV applications, but less useful for LEDs emitting light at visible wavelengths. For band gaps narrower than GaN, the InGaN ternary represents the narrowest band gap achievable in the aluminum, gallium, indium, and nitrogen materials system at a given lattice constant.
  • Dashed lines 22a-22d illustrate quaternary alloys of boron, gallium, indium, and nitrogen with 10% BN for different band gap bowing parameters B, assuming a band gap energy of wurtzite boron nitride (BN) of 5.5 eV.
  • line 22d O.
  • the band gap bowing parameter B in boron, gallium, indium, and nitrogen alloys appears to be non-zero, perhaps as large as 9 eV.
  • the addition of boron to InGaN layers reduces the band gap, and may permit growth of quaternary BInGaN layers that are lattice-matched to GaN and have smaller band gaps than GaN.
  • boron is added to the active region of the device, to reduce the lattice constant in the active region for a given band gap energy in the light emitting layers of the active region.
  • boron-containing layers may be latticed-matched to GaN.
  • Such compositions are illustrated by dashed line 27 in Fig. 5.
  • Quaternary alloys of boron, indium, gallium, and nitrogen on the right side of line 27 are in compression when grown on GaN.
  • Quaternary alloys of boron, indium, gallium, and nitrogen on the left side of line 27 are in tension when grown on GaN.
  • the amount of boron in any layer in the device is limited such that the layer is in compression when grown on GaN.
  • Possible quaternary alloys of boron, indium, gallium, and nitrogen in such embodiments are represented by the triangle between lines 26 and 27.
  • a conventional Ill-nitride device that emits blue light, or light with a wavelength between 430 and 480 nm, may have an InGaN light emitting layer with an InN composition between, for example, 10% and 14%.
  • an Ino I2 Ga 0 ssN light emitting layer has a bulk a-lattice constant of 3.23 A.
  • the light emitting layers in such a device are typically grown over a GaN layer with a lattice constant of about 3.189 A, and thus have an in-plane a-lattice constant of 3.189 A.
  • the amount of strain in the light emitting layers of such a device is the difference between the in-plane and bulk lattice constants in the light emitting layer, divided by the bulk lattice constant, or
  • at least one light emitting layer in a blue-emitting device is BInGaN.
  • the amount of BN in the light emitting layer is selected such that the band gap energy or emission color of the light emitting layers is the same as in the conventional blue-emitting device described above, but with a smaller bulk lattice constant in the light emitting layer, and therefore less strain.
  • the amount of BN in the light emitting layer might be selected such that the strain is less than 1% in some embodiments, less than 0.5% in some embodiments.
  • the BN composition x added to the above-described blue-emitting InGaN light emitting layer, resulting in a light emitting layer with the composition B x (In y Gai_ y )i_ x N may be, for example, 0 ⁇ x ⁇ 0.1 in some embodiments, 0.06 ⁇ x ⁇ 0.08 in some embodiments.
  • a conventional Ill-nitride device that emits cyan light, or light with a wavelength between 480 and 520 nm may have an InGaN light emitting layer with an InN composition between, for example, 14% and 18%.
  • the amount of strain in an Ino l ⁇ Gao 84 N light emitting layer grown on GaN is about 1.7%.
  • at least one light emitting layer in a cyan-emitting device is BInGaN.
  • the amount of BN in the light emitting layer might be selected such that the band gap or emission color of the light emitting layer is the same, and the strain is less than 1.5% in some embodiments, less than 1% in some embodiments.
  • the BN composition x added to the above-described cyan-emitting InGaN light emitting layer, resulting in a light emitting layer with the composition B x (In y Gai_ y )i_ x N, may be, for example, 0 ⁇ x ⁇ 0.12 in some embodiments, 0.08 ⁇ x ⁇ 0.11 in some embodiments.
  • a conventional Ill-nitride device that emits green light, or light with a wavelength between 520 and 560 nm may have an InGaN light emitting layer with an InN composition between, for example, 18% and 22%.
  • the amount of strain in an Ino 2 Gao sN light emitting layer grown on GaN is about 2.1%.
  • at least one light emitting layer in a green-emitting device is BInGaN.
  • the amount of BN in the light emitting layer might be selected such that the band gap or emission color of the light emitting layer is the same, and the strain is less than 2% in some embodiments, less than 1% in some embodiments.
  • the BN composition x added to the above-described green- emitting InGaN light emitting layer, resulting in a light emitting layer with the composition B x (In y Gai_ y )i_ x N may be, for example, 0 ⁇ x ⁇ 0.14 in some embodiments, 0.11 ⁇ x ⁇ 0.13 in some embodiments.
  • BN is incorporated in at least one of the barrier layers in a multiple quantum well device
  • the amount of BN is selected such that the band gap in the barrier layer is large enough to confine carriers in the light emitting layers and strain in the barrier layer or the light emitting layers is reduced as compared to a device with no boron in the barrier layers.
  • Fig. 8 is a plot of BN composition as a function of InN composition for BInGaN layers that are lattice-matched to GaN.
  • the x-axis represents an In x Gai_ x N composition on which the (BN) y (In x Gai_ x N)i_ y alloy is based.
  • the y-axis represents the BN composition in the (BN) y (In x Gai_ x N)i_ y alloy.
  • composition of BN in any boron-containing layers in devices according to embodiments of the invention is kept small enough that the boron-containing layers are wurtzite layers. At high enough BN composition, Ill-nitride layers may become zincblende.
  • BInGaN may be grown, for example, over Ill-nitride layers grown on a c-axis oriented sapphire substrate, in a low-pressure MOVPE reactor with 100% nitrogen as a carrier gas.
  • Triethylboron, trimethylindium, trimethylgallium, and ammonia may be used as precursors.
  • Other boron precursors may be used, such as trimethylboron, borane, di-borane, and boron metal. Optimized growth procedures for boron-containing nitrides are described in A. Ougazzaden et al., J. Cryst. Growth 298, 428 (2007), which is incorporated herein by reference.
  • Incorporating BN into one or more layers of a Ill-nitride device may be advantageous.
  • Wurtzite Ill-nitride layers exhibit large polarization, which include both a spontaneous component that is a function of temperature and composition, and a piezoelectric component, which is a function of strain in the layer.
  • Polarization discontinuities at the interface between layers of different composition result in polarization- induced sheet charges and electric fields.
  • the addition of BN may reduce the polarization discontinuity at a GaN/BInGaN interface relative to a GaN/InGaN interface, for example by reducing the strain at the interface.
  • selecting the appropriate BN composition may permit strain, band gap energy, and polarization may be at least partially decoupled, such that any two can be set arbitrarily at the expense of the third.
  • selecting the appropriate BN composition may permit strain, band gap energy, and polarization may be at least partially decoupled, such that any two can be set arbitrarily at the expense of the third.
  • a conventional GaN/InGaN/GaN heterostructure only one of strain, band gap energy, and polarization can be independently varied. Reducing the strain in a device by adding BN may permit grown of thicker active regions at higher InN composition.
  • the semiconductor structures illustrated and described above may be included in any suitable configuration of a light emitting device, such as a device with contacts formed on opposite sides of the device or a device with both contacts formed on the same side of the device.
  • a light emitting device such as a device with contacts formed on opposite sides of the device or a device with both contacts formed on the same side of the device.
  • the device may be formed either with transparent contacts and mounted such that light is extracted either through the same side on which the contacts are formed, or with reflective contacts and mounted as a flip chip, where light is extracted from the side opposite the side on which the contacts are formed.
  • the contact may include a small, thick, absorbing metal bond pad formed over a thin, transparent current spreading layer.
  • the current spreading layer may be, for example, a thin layer of Ni and/or Au, indium tin oxide, Cu-doped InO, ZnO, Ga-doped ZnO, or any other suitable doped, transparent oxide.
  • Fig. 6 illustrates a portion of one example of a suitable configuration, a flip chip device from which the growth substrate has been removed.
  • a portion of p-type region 18 and light emitting region 16 is removed to form a mesa that exposes a portion of n-type region 14.
  • N- and p-contacts 44 and 42 are formed on the exposed parts of n-type region 14 and p-type region 18, for example by evaporating or plating. Contacts 42 and 44 may be electrically isolated from each other by air or a dielectric layer.
  • a wafer of devices may be diced into individual devices, then each device may be flipped relative to the growth direction and mounted on a mount 40, in which case mount 40 may have a lateral extent larger than that of the device.
  • a wafer of devices may be connected to a wafer of mounts, then diced into individual devices.
  • Mount 40 may be, for example, semiconductor such as Si, metal, or ceramic such as AlN, and may have at least one metal pad (not shown) which electrically connects to p-contacts 42 and at least one metal pad (not shown) which electrically connects to the n-contacts 44.
  • Interconnects such as solder or gold stud bumps, connect the semiconductor device to mount 40.
  • Inter-metal dielectrics may be formed on or within mount 40 to electrically isolate the p-type and n-type current paths.
  • the growth substrate is removed by a process suitable to the substrate material, such as etching or laser melting.
  • a sacrificial semiconductor layer (not shown) can be selectively etched to lift off the substrate.
  • a rigid underfill may be provided between the device and mount 40 before or after mounting to support the semiconductor layers and prevent cracking during substrate removal.
  • a portion of the semiconductor structure may be removed by thinning after removing the substrate.
  • first single crystal layer 12 may remain in the finished device, as shown in Fig. 6, or they may be removed by thinning.
  • the exposed surface of the semiconductor structure may be roughened, for example by an etching process such as photoelectrochemical etching or by a mechanical process such as grinding.
  • Roughening the surface from which light is extracted may improve light extraction from the device.
  • a photonic crystal structure may be formed in the top surface of the semiconductor structure exposed by removing the grown substrate.
  • a structure 30 such as a phosphor layer or secondary optics known in the art such as dichroics or polarizers may be applied to the emitting surface.
  • Fig. 7 is an exploded view of a packaged light emitting device, as described in more detail in U.S. Patent 6,274,924.
  • a heat-sinking slug 100 is placed into an insert-molded leadframe.
  • the insert-molded leadframe is, for example, a filled plastic material 105 molded around a metal frame 106 that provides an electrical path.
  • Slug 100 may include an optional reflector cup 102.
  • the light emitting device die 104 which may be any of the devices described in the embodiments above, is mounted directly or indirectly via a thermally conducting submount 103 to slug 100.
  • a cover 108 which may be an optical lens, may be added.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biophysics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Led Devices (AREA)

Abstract

Embodiments of the invention include a Ill-nitride semiconductor structure comprising a light emitting region (16) disposed between an n-type region (14) and a p-type region. At least one layer in the light emitting region (18) is Bx(InyGa1-y)1-xN. In some embodiments, x is less than 14%. In some embodiments, the BN composition is selected such that the Bx(InyGa1-y)1- XN layer has the same band gap energy as a comparable InGaN layer, with a bulk lattice constant that is the same or smaller than the comparable InGaN layer.

Description

III-NITRIDE LIGHT EMITTING DEVICE INCORPORATING BORON
FIELD OF THE INVENTION
[0001] This invention relates to the field of semiconductor light emitting devices, and more specifically to Ill-nitride light emitting devices.
BACKGROUND
[0002] Semiconductor light-emitting devices including light emitting diodes (LEDs), resonant cavity light emitting diodes (RCLEDs), vertical cavity laser diodes (VCSELs), and edge emitting lasers are among the most efficient light sources currently available. Materials systems currently of interest in the manufacture of high-brightness light emitting devices capable of operation across the visible spectrum include Group III -V semiconductors, particularly binary, ternary, and quaternary alloys of gallium, aluminum, indium, and nitrogen, also referred to as Ill-nitride materials. Typically, Ill-nitride light emitting devices are fabricated by epitaxially growing a stack of semiconductor layers of different compositions and dopant concentrations on a sapphire, silicon carbide, Ill-nitride, composite, or other suitable substrate by metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), or other epitaxial techniques. The stack often includes one or more n- type layers doped with, for example, Si, formed over the substrate, one or more light emitting layers in an active region formed over the n-type layer or layers, and one or more p-type layers doped with, for example, Mg, formed over the active region. Electrical contacts are formed on the n- and p-type regions.
[0003] Ill-nitride devices are often grown on sapphire or SiC substrates. In conventional devices, an n-type GaN region is grown on the substrate, followed by an InGaN active region, followed by an AlGaN or GaN p-type region. The difference in lattice constant between the non-III-nitride substrate and the III -nitride layers, as well as the difference in lattice constant between Ill-nitride layers of different composition, causes strain in the device. The strain energy due to lattice mismatch can cause defects and decomposition of the InGaN active region, which may cause poor device performance. Since the strain energy is a function of both the composition of the InGaN light emitting layer (which determines the amount of strain) and the thickness of the light emitting layer, both the thickness and composition are limited in conventional Ill-nitride devices.
[0004] Ougazzaden et al. Bandgap bowing in BGaN thin films, Applied Physics Letters 93, 083118 (2008) reports on "thin films of BxGai_xN grown on AlN/sapphire substrates using metal-organic vapor phase epitaxy." See, for example, Abstract. "Ternary and quaternary layers of nitrides are important for bandgap engineering of GaN-based optoelectronic devices. The introduction of boron, which is a 'light' element, could, in principle, compensate for the strain induced by a high fraction of 'heavy' indium in InGaN-based light emitters and could provide lattice matching for BGaN grown on AlN and SiC substrates." See, for example, the first paragraph in the first column on the first page of Ougazzaden et al.
SUMMARY
[0005] An object of the invention is to provide a III -nitride device where at least one layer in the light emitting region includes boron. Embodiments of the invention include a III- nitride semiconductor structure comprising a light emitting region disposed between an n-type region and a p-type region. At least one layer in the light emitting region is Bx(InyGai_y)i_xN. The Bx(InyGai_y)i_xN layer has a band gap energy and a bulk lattice constant corresponding to a lattice constant of a relaxed layer having a same composition as the Bx(InyGai_y)i_xN light emitting layer. An InGaN layer having a same band gap energy as the Bx(InyGai_y)i_xN layer has a bulk lattice constant corresponding to a lattice constant of a relaxed layer having a same composition as the InGaN layer. The bulk lattice constant of the Bx(InyGai_y)i_xN layer is less than the bulk lattice constant of the InGaN layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Fig. 1 illustrates a portion of a III -nitride light emitting device according to embodiments of the invention.
[0007] Figs. 2, 3, and 4 are plots of ideal band gap energy as a function of position for portions of Ill-nitride devices according to embodiments of the invention.
[0008] Fig. 5 is a plot of band gap energy as a function of lattice constant for binary, ternary, and quaternary alloys of aluminum, boron, gallium, indium, and nitrogen.
[0009] Fig. 6 is a cross sectional view of a portion of a Ill-nitride device mounted in flip chip configuration on a mount.
[0010] Fig. 7 is an exploded view of a packaged light emitting device.
[0011] Fig. 8 is a plot of BN composition as a function of InN composition for BInGaN layers that are lattice-matched to GaN.
DETAILED DESCRIPTION
[0012] In accordance with embodiments of the invention, boron is incorporated into one or more layers of a Ill-nitride device. Incorporating boron into layers of a Ill-nitride device, particularly in the active region of the device, may reduce the strain in the device, which may improve the performance of the device.
[0013] Fig. 1 illustrates an embodiment of the invention. A first single crystal layer 12 is grown over a suitable growth substrate 10. The first single crystal layer 12 determines the lattice constant of all the Ill-nitride layers grown over it. The composition and growth conditions of first single crystal layer 12 may determine the lattice constant. An active or light emitting region 16 is grown over the first single crystal layer 12, sandwiched between an n-type region 14 and a p-type region 18.
[0014] N-type region 14 and first single crystal layer 12 may include multiple layers of different compositions and dopant concentration including, for example, preparation layers such as buffer layers or nucleation layers grown before or after first single crystal layer 12, which may be n-type or not intentionally doped, release layers designed to facilitate later release of the growth substrate or thinning of the semiconductor structure after substrate removal, and n- or even p-type device layers designed for particular optical or electrical properties desirable for the light emitting region to efficiently emit light. In some embodiments, a portion of n-type region 14 closest to the growth substrate is the first single crystal layer grown in the device, and a separate first single crystal layer 12 is omitted.
[0015] P-type region 18 is grown over light emitting region 16. Like the n-type region, the p-type region may include multiple layers of different composition, thickness, and dopant concentration, including layers that are not intentionally doped, or n-type layers.
[0016] Active region 16 is grown over n-type region 14. Examples of suitable light emitting regions, as described below, include a single thick or thin light emitting layer, or a multiple quantum well light emitting region including multiple thin or thick quantum well light emitting layers separated by barrier layers. For example, a multiple quantum well light emitting region may include multiple light emitting layers, each with a thickness of 25 A or less, separated by barriers, each with a thickness of 100 A or less.
[0017] In some embodiments, the thickness of each of the light emitting layers in the device is thicker than 50 A. In some embodiments, the light emitting region of the device is a single, thick light emitting layer with a thickness between 50 and 600 A, more preferably between 100 and 400 A. The optimal thickness may depend on the number of defects within the light emitting layer. The concentration of defects in the light emitting region is limited to less than 109 cm"2 in some embodiments, to less than 108 cm"2 in some embodiments, to less than 107 cm"2 in some embodiments, and to less than 106 cm"2 in some embodiments.
[0018] In some embodiments, at least one light emitting layer in the device is doped with a dopant such as Si to a dopant concentration between IxIO18 cm"3 and IxIO20 cm"3. Si doping may further reduce the strain in the light emitting layer. In some embodiments, the light emitting layer or layers are not intentionally doped.
[0019] Figs. 2-4 illustrate ideal band gap as a function of position for portions of light emitting devices according to embodiments of the invention. The band gaps illustrated are ideal, and therefore a function of composition only. Effects in real devices which may distort the band gap diagram, such as polarization, are not illustrated in Figs. 2-4.
[0020] In the device illustrated in Fig. 2, active region 16 includes a single light emitting layer. The light emitting layer may be a quaternary alloy of boron, indium, gallium, and nitrogen. The boron and indium composition are selected for the desired band gap in the light emitting layer, which determines the wavelength of emitted light. The portion of n-type region 14 adjacent active region 16 may be, for example, GaN or InGaN. The portion of p- type region 18 adjacent active region 16 may be, for example, GaN, InGaN, or AlGaN. The composition of n-type region 14 and p-type region 18 are selected such that the change in band gap between n-type region 14 and active region 16, and between active region 16 and p- type region 18, sufficiently confines electrons and holes in the active region. The difference between the band gap energy in the light emitting layers of active region 16 and the portions of n- and p-type regions 14 and 18 immediately adjacent the active region may be at least several times kT, which is 0.026 eV at room temperature. For example, the difference may be at least 0.1 eV in some embodiments, at least 0.15 eV in some embodiments.
[0021] In the device illustrated in Fig. 3, active region 16 includes a single light emitting layer, as described above in reference to Fig. 2. The composition in one or both of the n-type region and the p-type region adjacent the light emitting layer is graded. For example, the portion of n-type region 14 adjacent graded region 14a may be GaN. In graded region 14a, the composition may be graded from GaN to InGaN to the BInGaN composition in light emitting layer 16. Similarly, the portion of p-type region 18 adjacent graded region 18a may be GaN. In graded region 18a, the composition may be graded from the BInGaN composition in light emitting layer 16 to InGaN to GaN. The composition profile on either side of the active region 16 need not be symmetrical as illustrated in Fig. 3, and any graded region need not be linearly graded, as illustrated in Fig. 3. In some embodiments, the composition on only one side of active region 16 is graded. In some embodiments, a graded region as illustrated in Fig. 3 is combined with a step change in composition, as illustrated in Fig. 2. For example, the composition may be graded from GaN to InGaN in graded region 14a, then changed from InGaN to the BInGaN composition in active region 16 in a step change.
[0022] In the device illustrated in Fig. 4, active region 16 is a multiple quantum well active region with quantum well layers separated by one or more barrier layers. Though three quantum well layers 16a and two barriers 16b are shown in Fig. 4, more or fewer quantum well layers may be included in active region 16. Quantum wells 16a may be BInGaN, where the boron and indium compositions are selected for the desired band gap in the light emitting layer. Barrier layers 16b may be GaN, or InGaN at an indium composition having a band gap larger than the band gap in quantum wells 16a. Alternatively, quantum wells 16a may be InGaN and barrier layers 16b may be BInGaN with a boron and indium composition selected to have a band gap larger than the band gap in quantum wells 16a.
[0023] The multiple quantum well active region illustrated in Fig. 4 may be combined with graded composition n- and/or p-type regions, as described above in the text accompanying Fig. 3.
[0024] A Ill-nitride layer in a device may be characterized by lattice constant. As used herein, the "in-plane" lattice constant refers to the actual lattice constant of a layer within the device. The "bulk" lattice constant refers to an ideal lattice constant of relaxed, free-standing material of a given composition. When the in-plane and bulk lattice constants of a layer are the same, the layer is relaxed, or free of strain. The amount of strain in a layer is defined as: strain = | ε = I (a^i^e - at,uik) I / at,uik- Though this equation refers to the a-lattice constant and thus defines the strain in c-plane wurtzite, in wurtzite layers of other orientations, strain may be measured using lattice constants other than the a-lattice constant, or using more than one lattice constant. Layers may be lattice-matched for one lattice constant, and strained for another lattice constant.
[0025] In some embodiments, the composition in BInGaN light emitting layers are selected to have a bulk lattice constant that matches or is close to the in-plane lattice constant of first single crystal layer 12, shown in Fig. 1. First single crystal layer 12 is often GaN, with an in-plane a-lattice constant of about 3.189 A.
[0026] The band gap Eg of an alloy AxBi_xC may be expressed by:
Eg ABC = xEg AC + (l-x)Eg BC + x(l-x)B,
where B is band gap bowing parameter, which describes any non-zero curvature of a band gap vs. composition line. When the bowing parameter is zero, the relationship between band gap and composition is referred to as a Vegard's law relationship. Ternary alloys of aluminum, indium, gallium, and nitrogen (i.e., alloys that do not contain boron) at low indium compositions (for example, less than 30% InN) have bulk lattice constants that typically follow Vegard's law.
[0027] Fig. 5 is a plot of lattice constant as a function of band gap energy for several III- nitride alloys. GaN, and ternary alloys of aluminum, gallium, indium, and nitrogen are represented by lines 24 and 26. Shaded region 20 represents quaternary alloys of aluminum, gallium, indium, and nitrogen. While it is possible to grown AlGaInN alloys that are lattice matched to GaN, as illustrated in Fig. 5, they all have band gaps larger than GaN, making them potentially useful for UV applications, but less useful for LEDs emitting light at visible wavelengths. For band gaps narrower than GaN, the InGaN ternary represents the narrowest band gap achievable in the aluminum, gallium, indium, and nitrogen materials system at a given lattice constant.
[0028] Dashed lines 22a-22d illustrate quaternary alloys of boron, gallium, indium, and nitrogen with 10% BN for different band gap bowing parameters B, assuming a band gap energy of wurtzite boron nitride (BN) of 5.5 eV. Line 22a represents B = 9 eV, line 22b represents B = 3 eV, line 22c represents B = I eV, and line 22d represents B = O. Unlike aluminum, gallium, indium, and nitrogen alloys, which typically exhibit a Vegard's law relationship between band gap and composition, the band gap bowing parameter B in boron, gallium, indium, and nitrogen alloys appears to be non-zero, perhaps as large as 9 eV. As illustrated by lines 22a-22d in Fig. 5, however, at relatively small boron compositions, the addition of boron to InGaN layers reduces the band gap, and may permit growth of quaternary BInGaN layers that are lattice-matched to GaN and have smaller band gaps than GaN.
[0029] As illustrated in Fig. 5, the addition of BN to an InGaN alloy reduces the lattice constant. In some embodiments, boron is added to the active region of the device, to reduce the lattice constant in the active region for a given band gap energy in the light emitting layers of the active region. In some embodiments, boron-containing layers may be latticed-matched to GaN. Such compositions are illustrated by dashed line 27 in Fig. 5. Quaternary alloys of boron, indium, gallium, and nitrogen on the right side of line 27 are in compression when grown on GaN. Quaternary alloys of boron, indium, gallium, and nitrogen on the left side of line 27 are in tension when grown on GaN. In some embodiments, the amount of boron in any layer in the device is limited such that the layer is in compression when grown on GaN. Possible quaternary alloys of boron, indium, gallium, and nitrogen in such embodiments are represented by the triangle between lines 26 and 27.
[0030] For example, a conventional Ill-nitride device that emits blue light, or light with a wavelength between 430 and 480 nm, may have an InGaN light emitting layer with an InN composition between, for example, 10% and 14%. One example, an Ino I2Ga0 ssN light emitting layer, has a bulk a-lattice constant of 3.23 A. The light emitting layers in such a device are typically grown over a GaN layer with a lattice constant of about 3.189 A, and thus have an in-plane a-lattice constant of 3.189 A. The amount of strain in the light emitting layers of such a device is the difference between the in-plane and bulk lattice constants in the light emitting layer, divided by the bulk lattice constant, or |(3.189 A - 3.23 A)|/3.23 A x 100%, about 1.23%. In some embodiments of the invention, at least one light emitting layer in a blue-emitting device is BInGaN. The amount of BN in the light emitting layer is selected such that the band gap energy or emission color of the light emitting layers is the same as in the conventional blue-emitting device described above, but with a smaller bulk lattice constant in the light emitting layer, and therefore less strain. For example, the amount of BN in the light emitting layer might be selected such that the strain is less than 1% in some embodiments, less than 0.5% in some embodiments. The BN composition x added to the above-described blue-emitting InGaN light emitting layer, resulting in a light emitting layer with the composition Bx(InyGai_y)i_xN, may be, for example, 0 < x < 0.1 in some embodiments, 0.06 < x < 0.08 in some embodiments.
[0031] A conventional Ill-nitride device that emits cyan light, or light with a wavelength between 480 and 520 nm, may have an InGaN light emitting layer with an InN composition between, for example, 14% and 18%. The amount of strain in an Ino lβGao 84N light emitting layer grown on GaN is about 1.7%. In some embodiments of the invention, at least one light emitting layer in a cyan-emitting device is BInGaN. The amount of BN in the light emitting layer might be selected such that the band gap or emission color of the light emitting layer is the same, and the strain is less than 1.5% in some embodiments, less than 1% in some embodiments. The BN composition x added to the above-described cyan-emitting InGaN light emitting layer, resulting in a light emitting layer with the composition Bx(InyGai_y)i_xN, may be, for example, 0 < x < 0.12 in some embodiments, 0.08 < x < 0.11 in some embodiments.
[0032] A conventional Ill-nitride device that emits green light, or light with a wavelength between 520 and 560 nm, may have an InGaN light emitting layer with an InN composition between, for example, 18% and 22%. The amount of strain in an Ino 2Gao sN light emitting layer grown on GaN is about 2.1%. In some embodiments of the invention, at least one light emitting layer in a green-emitting device is BInGaN. The amount of BN in the light emitting layer might be selected such that the band gap or emission color of the light emitting layer is the same, and the strain is less than 2% in some embodiments, less than 1% in some embodiments. The BN composition x added to the above-described green- emitting InGaN light emitting layer, resulting in a light emitting layer with the composition Bx(InyGai_y)i_xN, may be, for example, 0 < x < 0.14 in some embodiments, 0.11 < x < 0.13 in some embodiments.
[0033] In embodiments where BN is incorporated in at least one of the barrier layers in a multiple quantum well device, the amount of BN is selected such that the band gap in the barrier layer is large enough to confine carriers in the light emitting layers and strain in the barrier layer or the light emitting layers is reduced as compared to a device with no boron in the barrier layers. Fig. 8 is a plot of BN composition as a function of InN composition for BInGaN layers that are lattice-matched to GaN. The x-axis represents an InxGai_xN composition on which the (BN)y(InxGai_xN)i_y alloy is based. The y-axis represents the BN composition in the (BN)y(InxGai_xN)i_y alloy.
[0034] The composition of BN in any boron-containing layers in devices according to embodiments of the invention is kept small enough that the boron-containing layers are wurtzite layers. At high enough BN composition, Ill-nitride layers may become zincblende.
[0035] BInGaN may be grown, for example, over Ill-nitride layers grown on a c-axis oriented sapphire substrate, in a low-pressure MOVPE reactor with 100% nitrogen as a carrier gas. Triethylboron, trimethylindium, trimethylgallium, and ammonia may be used as precursors. Other boron precursors may be used, such as trimethylboron, borane, di-borane, and boron metal. Optimized growth procedures for boron-containing nitrides are described in A. Ougazzaden et al., J. Cryst. Growth 298, 428 (2007), which is incorporated herein by reference.
[0036] Incorporating BN into one or more layers of a Ill-nitride device may be advantageous. Wurtzite Ill-nitride layers exhibit large polarization, which include both a spontaneous component that is a function of temperature and composition, and a piezoelectric component, which is a function of strain in the layer. Polarization discontinuities at the interface between layers of different composition result in polarization- induced sheet charges and electric fields. The addition of BN may reduce the polarization discontinuity at a GaN/BInGaN interface relative to a GaN/InGaN interface, for example by reducing the strain at the interface. In an n-GaN/BInGaN light emitting layer/p-GaN double heterostructure according some embodiments, selecting the appropriate BN composition may permit strain, band gap energy, and polarization may be at least partially decoupled, such that any two can be set arbitrarily at the expense of the third. In a conventional GaN/InGaN/GaN heterostructure, only one of strain, band gap energy, and polarization can be independently varied. Reducing the strain in a device by adding BN may permit grown of thicker active regions at higher InN composition.
[0037] The semiconductor structures illustrated and described above may be included in any suitable configuration of a light emitting device, such as a device with contacts formed on opposite sides of the device or a device with both contacts formed on the same side of the device. When both contacts are disposed on the same side, the device may be formed either with transparent contacts and mounted such that light is extracted either through the same side on which the contacts are formed, or with reflective contacts and mounted as a flip chip, where light is extracted from the side opposite the side on which the contacts are formed. In devices where light is extracted through the surface on which the contacts are formed, since current does not spread as readily in p-type Ill-nitride material as in n-type Ill-nitride material, the contact may include a small, thick, absorbing metal bond pad formed over a thin, transparent current spreading layer. The current spreading layer may be, for example, a thin layer of Ni and/or Au, indium tin oxide, Cu-doped InO, ZnO, Ga-doped ZnO, or any other suitable doped, transparent oxide.
[0038] Fig. 6 illustrates a portion of one example of a suitable configuration, a flip chip device from which the growth substrate has been removed. A portion of p-type region 18 and light emitting region 16 is removed to form a mesa that exposes a portion of n-type region 14. Though one via exposing n-type region 14 is shown in Fig. 6, it is to be understood that multiple vias may be formed in a single device. N- and p-contacts 44 and 42 are formed on the exposed parts of n-type region 14 and p-type region 18, for example by evaporating or plating. Contacts 42 and 44 may be electrically isolated from each other by air or a dielectric layer.
[0039] After contact metals 42 and 44 are formed, a wafer of devices may be diced into individual devices, then each device may be flipped relative to the growth direction and mounted on a mount 40, in which case mount 40 may have a lateral extent larger than that of the device. Alternatively, a wafer of devices may be connected to a wafer of mounts, then diced into individual devices. Mount 40 may be, for example, semiconductor such as Si, metal, or ceramic such as AlN, and may have at least one metal pad (not shown) which electrically connects to p-contacts 42 and at least one metal pad (not shown) which electrically connects to the n-contacts 44. Interconnects (not shown) such as solder or gold stud bumps, connect the semiconductor device to mount 40. Inter-metal dielectrics may be formed on or within mount 40 to electrically isolate the p-type and n-type current paths.
[0040] After mounting, the growth substrate is removed by a process suitable to the substrate material, such as etching or laser melting. For example, a sacrificial semiconductor layer (not shown) can be selectively etched to lift off the substrate. A rigid underfill may be provided between the device and mount 40 before or after mounting to support the semiconductor layers and prevent cracking during substrate removal. A portion of the semiconductor structure may be removed by thinning after removing the substrate. For example, first single crystal layer 12 may remain in the finished device, as shown in Fig. 6, or they may be removed by thinning. The exposed surface of the semiconductor structure may be roughened, for example by an etching process such as photoelectrochemical etching or by a mechanical process such as grinding. Roughening the surface from which light is extracted may improve light extraction from the device. Alternatively, a photonic crystal structure may be formed in the top surface of the semiconductor structure exposed by removing the grown substrate. A structure 30 such as a phosphor layer or secondary optics known in the art such as dichroics or polarizers may be applied to the emitting surface.
[0041] Fig. 7 is an exploded view of a packaged light emitting device, as described in more detail in U.S. Patent 6,274,924. A heat-sinking slug 100 is placed into an insert-molded leadframe. The insert-molded leadframe is, for example, a filled plastic material 105 molded around a metal frame 106 that provides an electrical path. Slug 100 may include an optional reflector cup 102. The light emitting device die 104, which may be any of the devices described in the embodiments above, is mounted directly or indirectly via a thermally conducting submount 103 to slug 100. A cover 108, which may be an optical lens, may be added.
[0042] Having described the invention in detail, those skilled in the art will appreciate that, given the present disclosure, modifications may be made to the invention without departing from the spirit of the inventive concept described herein. Therefore, it is not intended that the scope of the invention be limited to the specific embodiments illustrated and described.

Claims

CLAIMSWhat is being claimed is:
1. A structure comprising: a Ill-nitride semiconductor structure comprising a light emitting region disposed between an n-type region and a p-type region, wherein: at least one layer in the light emitting region is Bx(InyGai_y)i_xN; the Bx(InyGai_y)i_xN layer has a band gap energy and a bulk lattice constant corresponding to a lattice constant of a relaxed layer having a same composition as the Bx(InyGai_y)i_xN light emitting layer; an InGaN layer having a same band gap energy as the Bx(InyGai_y)i_xN layer has a bulk lattice constant corresponding to a lattice constant of a relaxed layer having a same composition as the InGaN layer; and the bulk lattice constant of the Bx(InyGai_y)i_xN layer is less than the bulk lattice constant of the InGaN layer.
2. The structure of claim 1 wherein 0 < x < 0.14.
3. The structure of claim 1 wherein 0 < x < 0.1.
4. The structure of claim 1 wherein the at least one Bx(InyGai_y)i_xN is a light emitting layer.
5. The structure of claim 4 wherein 0.06 < x < 0.08 and 0.1 < y < 0.14.
6. The structure of claim 4 wherein 0.08 < x < 0.11 and 0.14 < y < 0.18.
7. The structure of claim 4 wherein 0.11 < x < 0.13 and 0.18 < y < 0.22.
8. The structure of claim 1 wherein: the light emitting region comprises at least two quantum well light emitting layers separated by a barrier layer; and the at least one Bx(InyGai_y)i_xN is the barrier layer.
9. The structure of claim 1 wherein at least a portion of one of the n-type region and the p-type region in direct contact with the light emitting region has a graded composition.
10. The structure of claim 1 further comprising first and second electrical contacts electrically connected to the n-type and p-type regions.
11. The structure of claim 1 wherein the Bx(InyGai_y)i_xN layer is lattice-matched to GaN.
12. The structure of claim 1 wherein the Bx(InyGai_y)i_xN layer is in compression.
EP10704198.0A 2009-03-04 2010-02-04 Iii-nitride light emitting device incorporating boron Active EP2404311B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12/397,417 US8106403B2 (en) 2009-03-04 2009-03-04 III-nitride light emitting device incorporation boron
PCT/IB2010/050520 WO2010100572A1 (en) 2009-03-04 2010-02-04 Iii-nitride light emitting device incorporating boron

Publications (2)

Publication Number Publication Date
EP2404311A1 true EP2404311A1 (en) 2012-01-11
EP2404311B1 EP2404311B1 (en) 2017-04-12

Family

ID=42102372

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10704198.0A Active EP2404311B1 (en) 2009-03-04 2010-02-04 Iii-nitride light emitting device incorporating boron

Country Status (8)

Country Link
US (1) US8106403B2 (en)
EP (1) EP2404311B1 (en)
JP (1) JP5702739B2 (en)
KR (1) KR101732524B1 (en)
CN (1) CN102341887B (en)
RU (1) RU2523747C2 (en)
TW (1) TWI497753B (en)
WO (1) WO2010100572A1 (en)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5899519B2 (en) * 2009-11-05 2016-04-06 パナソニックＩｐマネジメント株式会社 Solid-state imaging device
US9178108B2 (en) * 2010-05-24 2015-11-03 Lg Innotek Co., Ltd. Light emitting device and light emitting device package
EP2408028B1 (en) * 2010-07-16 2015-04-08 LG Innotek Co., Ltd. Light emitting device
CN104412396B (en) 2012-07-05 2021-11-09 亮锐控股有限公司 Light-emitting diode with a nitrogen-and phosphorus-containing light-emitting layer
CN105358488A (en) * 2013-07-03 2016-02-24 皇家飞利浦有限公司 Light guiding member and light emitting arrangement
FR3050872B1 (en) * 2016-04-27 2019-06-14 Commissariat A L'energie Atomique Et Aux Energies Alternatives ELECTROLUMINESCENT DIODE COMPRISING AT LEAST ONE INTERMEDIATE LAYER OF LARGER GAP ARRANGED IN AT LEAST ONE BARRIER LAYER OF THE ACTIVE ZONE
CN108831978A (en) * 2018-04-24 2018-11-16 华灿光电(苏州）有限公司 A kind of LED epitaxial slice and its manufacturing method
CN109065679B (en) * 2018-06-29 2020-05-19 华灿光电（浙江）有限公司 Light emitting diode epitaxial wafer and manufacturing method thereof
CN109065682B (en) * 2018-06-29 2019-10-08 华灿光电（浙江）有限公司 A kind of LED epitaxial slice and its manufacturing method
CN109802020B (en) * 2018-12-26 2020-05-19 华灿光电（浙江）有限公司 GaN-based light emitting diode epitaxial wafer and preparation method thereof
CN109873061B (en) * 2019-01-08 2020-08-18 华灿光电（浙江）有限公司 Gallium nitride-based light emitting diode epitaxial wafer and manufacturing method thereof
CN109888068B (en) * 2019-01-23 2020-04-14 华灿光电（浙江）有限公司 Near ultraviolet light emitting diode epitaxial wafer and preparation method thereof
CN110061104B (en) * 2019-02-28 2020-08-14 华灿光电(苏州）有限公司 Method for manufacturing gallium nitride-based light emitting diode epitaxial wafer
CN112366257B (en) * 2020-09-27 2022-03-18 华灿光电（浙江）有限公司 Light emitting diode epitaxial wafer and preparation method thereof
CN115050870B (en) * 2022-08-12 2022-11-08 江西兆驰半导体有限公司 GaN-based light emitting diode epitaxial wafer and preparation method thereof
CN115172555B (en) * 2022-09-08 2022-11-18 江西兆驰半导体有限公司 Epitaxial wafer of high-luminous-efficiency light-emitting diode, preparation method of epitaxial wafer and light-emitting diode
CN116581215B (en) * 2023-07-10 2023-09-22 江西兆驰半导体有限公司 Light-emitting diode epitaxial wafer and manufacturing method thereof
CN117239025B (en) * 2023-11-15 2024-02-20 江西兆驰半导体有限公司 GaN-based green light LED epitaxial wafer, preparation method thereof and LED

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903364A (en) * 1974-08-23 1975-09-02 Ibm High resolution line scanner
JPH11261105A (en) * 1998-03-11 1999-09-24 Toshiba Corp Semiconductor light-emitting device
US6274924B1 (en) * 1998-11-05 2001-08-14 Lumileds Lighting, U.S. Llc Surface mountable LED package
JP2000196194A (en) * 1998-12-25 2000-07-14 Sanyo Electric Co Ltd Semiconductor light-emitting device
JP2000277860A (en) * 1999-03-24 2000-10-06 Sanyo Electric Co Ltd Semiconductor laser element
US6903364B1 (en) * 1999-03-26 2005-06-07 Matsushita Electric Industrial Co., Ltd. Semiconductor structures using a group III-nitride material system with reduced phase separation and method of fabrication
US6838705B1 (en) * 1999-03-29 2005-01-04 Nichia Corporation Nitride semiconductor device
DE60336252D1 (en) * 2002-08-29 2011-04-14 Seoul Semiconductor Co Ltd LIGHT-EMITTING COMPONENT WITH LIGHT-EMITTING DIODES
US7323721B2 (en) * 2004-09-09 2008-01-29 Blue Photonics Inc. Monolithic multi-color, multi-quantum well semiconductor LED
JP2009027022A (en) * 2007-07-20 2009-02-05 Rohm Co Ltd Nitride semiconductor light-emitting element

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010100572A1 *

Also Published As

Publication number Publication date
TWI497753B (en) 2015-08-21
RU2523747C2 (en) 2014-07-20
KR101732524B1 (en) 2017-05-04
US8106403B2 (en) 2012-01-31
EP2404311B1 (en) 2017-04-12
KR20110124337A (en) 2011-11-16
JP5702739B2 (en) 2015-04-15
JP2012519953A (en) 2012-08-30
CN102341887B (en) 2015-09-30
US20100224852A1 (en) 2010-09-09
CN102341887A (en) 2012-02-01
WO2010100572A1 (en) 2010-09-10
RU2011140129A (en) 2013-04-20
TW201041180A (en) 2010-11-16

Similar Documents

Publication Publication Date Title
US8106403B2 (en) III-nitride light emitting device incorporation boron
US10672949B2 (en) Light emitting device including porous semiconductor
US8847252B2 (en) III-nitride light emitting device with double heterostructure light emitting region
US7663148B2 (en) III-nitride light emitting device with reduced strain light emitting layer
US10304997B2 (en) III-nitride light emitting device with a region including only ternary, quaternary, and/or quinary III-nitride layers
US7221000B2 (en) Reverse polarization light emitting region for a semiconductor light emitting device
US20090032828A1 (en) III-Nitride Device Grown on Edge-Dislocation Template
US8945975B2 (en) Light emitting device grown on a relaxed layer
WO2010112980A1 (en) Iii-nitride light emitting device including porous semiconductor layer

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20111004

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: KONINKLIJKE PHILIPS N.V.

Owner name: PHILIPS LUMILEDS LIGHTING COMPANY LLC

17Q First examination report despatched

Effective date: 20151014

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602010041457

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: H01L0021020000

Ipc: H01L0033320000

RIC1 Information provided on ipc code assigned before grant

Ipc: B82Y 20/00 20110101ALI20161216BHEP

Ipc: H01L 33/06 20100101ALN20161216BHEP

Ipc: H01L 33/32 20100101AFI20161216BHEP

Ipc: H01L 21/02 20060101ALN20161216BHEP

Ipc: H01S 5/343 20060101ALI20161216BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

INTG Intention to grant announced

Effective date: 20170202

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 884682

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010041457

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170412

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 884682

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170412

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170713

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170712

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170712

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170812

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010041457

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602010041457

Country of ref document: DE

Owner name: LUMILEDS HOLDING B.V., NL

Free format text: FORMER OWNERS: KONINKLIJKE PHILIPS N.V., EINDHOVEN, NL; PHILIPS LUMILEDS LIGHTING COMPANY, LLC, SAN JOSE, CALIF, US

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

26N No opposition filed

Effective date: 20180115

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

Owner name: KONINKLIJKE PHILIPS N.V., NL

Effective date: 20180611

Ref country code: FR

Ref legal event code: CD

Owner name: LUMILEDS LLC, US

Effective date: 20180611

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

Owner name: LUMILEDS LLC, US

Effective date: 20180706

Ref country code: FR

Ref legal event code: CD

Owner name: KONINKLIJKE PHILIPS N.V., NL

Effective date: 20180706

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180204

REG Reference to a national code

Ref country code: FR

Ref legal event code: CA

Effective date: 20181026

Ref country code: FR

Ref legal event code: TP

Owner name: LUMILEDS HOLDING B.V., NL

Effective date: 20181026

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180228

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20190328 AND 20190402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20100204

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170412

Ref country code: MK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170412

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230530

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240228

Year of fee payment: 15

Ref country code: GB

Payment date: 20240220

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240226

Year of fee payment: 15